Color developer composition for color photography

ABSTRACT

A color development composition for color photography containing an aromatic primary amine developing agent and a cyan coupler represented by the following general formula   WHEREIN R represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group and X represents a member selected from the group consisting of a hydrogen atom and an acyl group.

United States Patent [72] Inventors Shiro Kimura;

Atsuaki Arai; Kimio Kishimoto; lsao Shimamura, all of Kanagawa, Japan [21] Appl. No. 696,774

[22] Filed Jan. 10, 1968 [45] Patented Oct. 26, 1971 [73] Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority Jan. 12, 1967 [33] Japan [54] COLOR DEVELOPER COMPOSITION FOR COLOR PHOTOGRAPHY 9 Claims, 1 Drawing Fig.

[52] US. Cl... 96/55 [51] Int. Cl G03c 7/00 [50] Field of Search 96/100, 55,

[56] References Cited UNITED STATES PATENTS 2,589,004 3/1952 Weissberger et a1 96/100 3,002,836 10/1961 Vittum et al 96/100 3,133,815 5/1964 Greenhalgh 3,418,121 12/1968 Yoshidaetal.

Primary Examiner.l. Travis Brown Attorney-Sughrue, Rothwell, Mion, Zinn & MacPeak NHCOR wherein R represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group and X represents a member selected from the group consisting of a hydrogen atom and an acyl group.

(PTICAL DENSITY PATENTEDnm 26 I97! WAVE LENGTH (mp) INVENTORS' SHIRO KIMURA ATSUAKI ARA! KIMIO KISHIMOTO ISAO SHIMAMURA BACKGROUND OF THE INVENTION 1 Field of the Invention The present invention relates generally to a color developer composition for color photography and more particularly to a color developer composition containing a novel cyan coupler having improved properties and an aromatic primary amine developing agent.

2. Description of the Prior Art In general, it has been known in color photographic processing to use cyan couplers, magenta couplers and yellow couplers forming eolored images by reaction with the oxidation products of aromatic primary amine developing agents and many patents have been granted for such couplers.

The dyes formed by the conventional color development using such couplers are insoluble in water, photographic developing solutions and fixing solutions, and silver images fonned during color development simultaneously with the dye images and unreacted silver halide are removed from photographic emulsion layers in subsequent processing to leave the dye images in the emulsion layers as pure colored images.

Couplers useful for color photography are generally required to form dyes by color development, having desired light transmittance or spectral absorption characteristics. Furthermore, a cyan or blue-green dye must, ideally, completely absorb red light and completely transmit blue light and green light. Also, it is necessary that the light transmitting property of these dyes be maintained for a long period of time and that the dyes have high fastness to light, heat and humidity, so' that the light transmitting property is not degraded. Further, other dyes used for color photography, such as. magenta and yellow dyes, must similarly have selective spectral absorption characteristics and light transmitting properties.

A coupler used for forming a cyan colored image is usually a phenol derivative or a naphthol derivative, and forms an indoaniline dye or an indophenol dye by oxidative coupling with a specific developing agent.

However, conventionally used cyan couplers usually show insufficient properties as above for color photography. That is, many of the naphthol couplers and substituted naphthol couplers used conventionally as cyan couplers for color photography have excessively high green and blue absorptions, while some of them do not have red absorption to a desirable extent. Moreover, in the case of employing such conventional cyan couplers, it frequently occurs that the silver image formed together with the formation of dye images by coupling is not completely removed from the emulsion layers in subsequent processings owing to the properties specific to the structure of the coupler or the dye formed. This results in markedly reducing the transparency of the dye images. Furthermore, there may be some cyan dyes showing a red absorption property to a desired extent, but many of them are undesirable in sight and in color reproduction as their absorption maximum is in too long a wave length region.

As a cyan coupler incorporated in a color development composition there are conventionally employed phenol derivatives or naphthol derivatives, and, among them, 2- benzyl-l-hydroxynaphthamide is known as a useful cyan coupler.

The inventors have found, as the result of various investigations, that 2-benzyl-1hydroxynaphthamide, 2-(pacetamidobenzyl)-l-hydroxynaphthamide, and 2-(macetamidobenzyl)-lhydroxynaphthamide are not suitable cyan couplers since the absorption maximum of the cyan dye image formed by the coupling of the coupler with the oxidation product of an aromatic primary amine developing agent is in an extremely long wave length region. Also, the dye image has a large quantity of unnecessary blue and green absorption and shows no desirable spectral absorption characteristics.

An object of this invention is to provide a color development composition containing an aromatic primary amine developing agent and a cyan coupler capable of forming a cyan dye having excellent spectral absorption characteristics necessary for forming desirable cyan colored images and having excellent silver removing property, light fastness, heat resistance and moisture resistance.

SUMMARY OF THE INVENTION Thus, the color development composition of the present invention contains an aromatic primary amine development agent and a cyan coupler represented by the general formula:

I NHC 0R wherein R represents a hydrogen atom, a methyl group or an ethyl group and X represents a hydrogen'atom or an acyl group.

As the cyan coupler represented by the above general formula, there are 2-(o-acylamidobenzyl)-lhydroxynaphtha- BRIEF DESCRIPTION OF THE DRAWING Now, it will be understood from the spectral absorption curves shown in the accompanying drawing that the cyan couplers shown above provide cyan dye images having excellent spectralabsorption characteristics. That is, in the drawing, there are shownthree spectral absorption curves.

A. the spectral absorption curve of the dye image formed by the oxidative coupling of the cyan coupler of this invention, 2- (o-acetamidobenzyl)-l-hydroxynaphthamide and a color developer, 2-methyl-4-(N-ethyl-N-fi-hydroxy ethyl)aminoaniline. I

B. the controlspectral absorption curve of the dye image obtained from a conventional cyan coupler, 2-benzyl-lhydroxynap'hthamideand the same color developer, and

C. the control spectral absorption curve of the dye image obtained from a conventional cyan coupler, 2(pacetamidoberizyD-l hydroxynaphthamide and the same color developer.

DETAILED DESCRIPTION OF THE INVENTION From the results shown in the drawing, it will be understood that the dye images obtained from the cyan coupler of this invention and the color developer have less undesirable absorptions in the region near 450-550 my. and also have the desired absorption maximum, that is, the dye image shows very excellent absorption characteristics. F Urthermore, while the cyan coupler of this invention, 2-(o-acetamidobenzyl)-lhydroxynaphthamide, has a chemical structure similar to that of a conventional cyan coupler, Z-benzyl-l-hydroxynaphthamide, the former is clearly different from the latter in property. That is, in the 'case'of using the cyan coupler of this invention, there can be obtained a cyan dye image having good light fastness, heat resistance and moisture resistance as well as an extremely high lightness since silver images can be easily and completely removed from the emulsion layers in the subsequent processingsa's compared with the case of using known 2-benzyl-l-hydroxynaphthamide as a cyan coupler. Such results are very preferable for obtaining dye images for color photography and it is unexpected that the cyan coupler used in the present invention would-have such profitable features.

TABLE Cyan Coupler Remaining Color Percent Z-(o-acetamidobenzyl)-l-hydroxynaphlhamide 98% Z-bcnzyl-l-hydroxynaphthamide 87% As is clear from the results shown in the table, it was confirmed that the cyan coupler of this invention has excellent light fastness as compared with conventional cyan couplers.

By the inventorsdetailed studies, it has been confirmed that particularly excellent properties of the dye formed by the oxidative coupling of the cyan coupler of this invention, such as, 2-(o-ametamidobenzyl)-l-hydroxynaphthamide and the color developer, 2-methyl-4-(N-ethyl-N-B-hydroxyethyl)aminoaniline, as compared with the dyes formed by the oxidative coupling of a conventional cyan coupler, such as, 2- benzyll -hydroxynaphthomide, 2-( p-acetamidobenzyl)- 1 hydroxynaphthamide or 2-(m-acetamidobenzyl)-l-hydroxynaphthamide, are caused by the easily combining properties of the dye molecules. That is, it has been confirmed that the dye molecules of the dye image formed by the color development in the silver halide emulsion using the color developer of this invention are not present in a single molecular state but in a state in which more than two molecules are combined, which provides preferable effects satisfying the various factors required for the cyan dye for color photography.

The same effects as in the case of using 2-(oacetomidobenzyl)-l-hydroxynaphthamide are also observed in the case of using 2-o-formamido-benzyl)-l-hydroxynaphthamide or 2-(o-propionamidobenzyl)-1-hydroxynaphthamide, as well as in the case of using the 2-(0- acylamidobenzyU-l-acyloxynaphthamide such as, 2-(0- acetomidobenzyl)-l-acetoxynaphthamide formed during the preparation of these cyan couplers.

The novel cyan couplers of this invention, 2-(0- acylamidobenzyl)- l -hydroxynaphtyamides and 2-( oacylamidobenzyl)-l-acyloxynaphthamides may be prepared as follows. In particular, the latter can be formed during the preparation of the former.

By a Gabriel reaction there was synthesized onitrobenzylamine from o-nitrobenzyl bromide prepared by bromizing o-nitrotoluene by the method of Southwick et al. (cf.; J. Chem. Soc. of America," Vol. 80, 1168). Then, the produce was melted together with 1-hydroxy-2-naphthoic acid phenyl ester by beating them in an oil bath to 180 C., to provide 2-(o-nitrobenzyl)-l-hydroxynaphthamide. The naphthamide thus obtained was subjected to a hydrogenation for 2 hours at a temperature of 50 C., and at a maximum hydrogen pressure of 50 atoms, in glacial acetic acid by using as the catalyst a 10 percent palladium-carbon system to provide 2- (o-aminobenzyl-l-hydroxynaphthamide, which was recrystal lized from ethanol to provide the yellow crystal thereof having a melting point of 143l44 C.

a. Preparation of 2-(o-acetamidobenzyl)-l-hydroxynaphthamide:

In acetic anhydride there was heated under refluxing 2-(0- aminobenzyl)-l-hydroxynaphthamide for 30 minutes and excess acetic anhydride was distilled off under a reduced pressure. There was dissolved in a 10 percent aqueous solution of sodium hydroxide Z-(o-acetamidobenzyl-l-acetoxynaphthamide having a melting point of 175 C., prepared above, and

the solution was neutralized with 10 percent hydrochloric acid to form a white precipitate, which was recovered and recrystallized from absolute ethanol to provide the colorless crystal of 2-(o-acetamidobenzyl)-l-hydroxynaphthamide having a melting point of 197 C.198 C. Nitrogen Analysis: Found 8.23 percent, Calculated 8.38 percent.

b. Preparation of 2(o-propionamidobenzyl)-l-hydroxynaphthamide:

The same procedure as the above case was repeated using 2-(o-aminobenzyl)-l-hydroxynaphthamide and propionic anhydride to provide 2-(o-propionamidobenzyl)-l-propionyloxynaphthamide having a melting point of 154 C.-l55 C. (decomposed), which was then partially hydrolyzed with a 10 percent aqueous sodium hydroxide solution to provide a white solid. The white solid was recrystallized from ethanol to give the colorless crystal thereof having a melting point of 196 C. Nitrogen analysis: Found 8.00 percent, Calculated 8.03 percent.

c. Preparation ynaphthamide: v

In percent formic acidthere was heated under refluxing 2-(o-aminobenzyl)-l-hydroxynaphthamide for 30 minutes and excessive formic acid was distilled off under a reduced pressure. The crystals thus obtained were processed as in the case of preparation (a) mentioned above to provide the subject compound as crystals having a melting point of C. Nitrogen analysis: Found 8.66 percent, Calculated 8.75 percent.

In addition, it has been confirmed that the 2-(0- acylamidobenzyl)-l-acyloxynaphthamide, i.e., the ON- diacetyl compound obtained during the aforesaid synthesis exhibits the same action as the corresponding free naphthol compounds, that is, the cyan compound of this invention, 2- (o-acylamidobenzyl)-l-hydroxynaphthamide, in a color developer composition for color photography.

The invention will further be explained by referring to the following examples.

of 2-(o-formamidobenzyl)- l -hydrox- EXAMPLE 1 A photographic light sensitive color film prepared by applying a conventional silver iodo-bromide red-sensitive emulsion to a film base, followed by drying, was red-exposed by a step wedge, developed for 3 minutes n a black and white developing composition, subjected to reversal exposure by red light, and then developed for 5 minutes in a cyan developing composition followed by water washing. The film thus processed was processed in a conventional silver bleaching bath and fixed in a fixing bath containing sodium thiosulfate to provide a positive image of a cyan dye. The spectral absorption curve of the colored image is shown in the accompanying drawing as Curve A.

The compositions of the black and white developing solution and cyan developing solution used in this example are as follows:

Black and White Developing Solution N-Methyl-p-Aminophenol-1/2 Sulfate 4.5 g. Sodium Sulfite 70 g. Hydroquinone 8 g. Sodium Carbonate (Mono-l-lydrate) 20 Potassium Bromide 2.5 g. Water to Make 1 l.

Cyan Developing Solution Potassium bromide 3 g. Sodium Sulfite 10 g Sodium Sulfate 50 5. Potassium Thiocyanate l g. Monobenzyl-p-Aminophenol 0.5 g. Methanol 10 ml p-Aminophenol 0.1 g. Sodium Hydroxide 3 g. Z-(o-Acetamidobcnzyl)-l-Hydroxynaphthamide 2 g. Hexylene Glycol 10 g. 2-Methyl-4-(N-Ethyl-N-fi-Hydroxyethyl)-Aminoaniline Water to Make EXAMPLE 2 A photographic light sensitive color film prepared by applying a conventional silver iodo-bromide red-sensitive emulsion to a film base, followed by drying, was red-exposed through a step wedge and the same procedure as in example 1 was repeated for the color film while using a cyan developing solution having the composition shown below, instead of the cyan developing solution in the example i, and a good positive Water To Make 1 1.

EXAMPLE 3 The same procedure as in example 1 was repeated while using a cyan developing solution having the following composition instead of the cyan developing solution as in example i and a good positive image of a cyan dye was obtained.

Potassium Bromide 2 g. Sodium Sulfite g. Sodium Carbonate 23 g. Sodium Hydroxide 1.5 g. 2-(o-Formamidobenzyl)-l-Hydroxynaphthamide 1.5 g. Hcxylerie Glycol 10 ml. 2-Methyl-4-(N-Ethyl-N-fl-Hydroxyethyl)-Aminoaniline Sulfate 2 g.

Water to Make 1 1.

EXAMPLE 4 The same procedure as in example 1 was repeated while using a cyan developing solution having the following composition instead of the cyan developing solution as in example 1 and a good positive image of a cyan dye was obtained.

Potassium Bromide 2 g. Sodium Sulfite 10 g. Sodium Hydroxide 1.5 g. Z-(o-Propionamidobcnzyl)-l-Hydroxynaphthamide 1.5 g. Sodium Carbonate 23 g. Hexylene Glycol 10 ml.

Z-MethyI-4-(N-Ethyl-N-B-Hydroxyethyl)-Aminoaniline Sulfate 2 g. Water to Make l l.

EXAMPLE 5 The same procedure as in example 1 was repeated while using a cyan developing solution having the following composition instead of the cyan developing solution as in example 1 and a good positive image of a cyan dye was obtained.

Potassium Bromide 2 g. Sodium Sulfite 10 g. Sodium Hydroxide 1,5 g. Z-(o-AcetamidobenzyI)-l-Acetoxynaphthamide l.5 g, Sodium Carbonate Hexylene Glycol 10 g.

2-Methyl-4-(N-Ethyl-N-B-Hydroxyethyl)-Aminoaniline Sulfate 2 g. Water to Make 1 1.

EXAMPLE 6 An exposed conventional multiple layer type photographic reversal color film was developed for 3 minutes in a black and white developing solution washed with water, subjected to a reversal exposure by red light, and then color developed for 4 minutes in a cyan color developing solution. The film was washed with water, blue-exposed, and developed for 4 minutes in a yellow developing solution followed by water washing. Thereafter, the film was developed for 2 minutes in a black and white developing solution, white-exposed, and developed for 4 minutes in a magenta developing solution. After water-washing, the film was silver-bleached by a conventional method and fixed in a fixing solution containing a sodium thiosulfate to provide a color photographic image.

The compositions of the cyan developing solution, the yellow developing solution and the magenta developing solution used in this example were as follows, and the composition of the black and white developing solution was the same as in example l.

Cyan Developing Solution Water to Make What is claimed is:

l. A color development composition for color photography containing an aromatic primary amine developing agent and a cyan coupler represented by the following general formula:

ox CONHCHlQ NHCOR wherein R represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group and X represents a member selected from the group consisting of a hydrogen atom and an acyl group.

2. The color development composition according to claim 1 wherein said cyan coupler is selected from the group consisting of 2-(-acetamidobenzyl)-l-hydroxynaphthamide, 2-(0- propionamidobenzyl)-l-hydroxynaphthamide, 2-(o-formamidobenzyl)- 1 -hydroxynaphthamide, 2-(0- acetamidobenzyD- l -acetoxynaphthamide, and 2-(0- propionamidobenzyl)-1-propionyloxynaphthamide.

3. The color development composition according to claim 1 wherein said aromatic primary amine developer is 2-methyl-4- (N-ethyl-N-B-hydroxyethyl)aminoaniline.

4. The color development composition according to claim 2 wherein said aromatic primary amine developer is 2-methyl-4- (N-ethyl-N-B-hydroxyethyl)aminoaniline.

5. The color development composition according to claim 1 wherein R is a hydrogen atom.

6. The color development composition according to claim 1 wherein R is a methyl group.

7. The color development composition according to claim 1 wherein R is an ethyl group.

8. The color development composition according to claim 1 wherein X is a hydrogen atom.

9. The color development composition according to claim 1 wherein X is an acyl group. 

2. The color development composition according to claim 1 wherein said cyan coupler is selected from the group consisting of 2-(o-acetamidobenzyl)-1-hydroxynaphthamide, 2-(o-propionamidobenzyl)-1-hydroxynaphthamide, 2-(o-formamidobenzyl)-1-hydroxynaphthamide, 2-(o-acetamidobenzyl)-1-acetoxynaphthamide, and 2-(o-propionamidobenzyl)-1-propionyloxynaphthamide.
 3. The color development composition according to claim 1 wherein said aromatic primary amine developer is 2-methyl-4-(N-ethyl-N- Beta -hydroxyethyl)aminoaniline.
 4. The color development composition according to claim 2 wherein said aromatic primary amine developer is 2-methyl-4-(N-ethyl-N- Beta -hydroxyethyl)aminoaniline.
 5. The color development composition according to claim 1 wherein R is a hydrogen atom.
 6. The color development composition according to claim 1 wherein R is a methyl group.
 7. The color development composition according to claim 1 wherein R is an ethyl group.
 8. The color development composition according to claim 1 wherein X is a hydrogen atom.
 9. The color development composition according to claim 1 wherein X is an acyl group. 